2,6-Dibromo-4-butyl­aniline

Zhao, L.; Feng, L.-P.

doi:10.1107/S1600536810047410

organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3268

https://doi.org/10.1107/S1600536810047410

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2,6-Dibromo-4-butylaniline

Liang Zhao ^a ^* and Li-Ping Feng ^a

^aDepartment of Chemical & Environmental Engineering, Anyang Institute of Technology, Anyang 455000, People's Republic of China
^*Correspondence e-mail: ayitzhao@yahoo.com.cn

(Received 12 November 2010; accepted 16 November 2010; online 24 November 2010)

In the title compound, C₁₀H₁₃Br₂N, the amino N atom is essentially coplanar with the benzene ring, with an r.m.s. deviation of 0.004 Å. Weak intramolecular N—H⋯Br hydrogen bonds occur. In the crystal, molecules are linked into a zigzag chain parallel to the b axis by weak N—H⋯N hydrogen bonds.

Related literature

For related compounds, see: Fender et al. (2002 ); Grabowski (2005 ); Kryatova et al. (2004 ); Lehn (1995 ); Pedersen (1967 ); Scheiner (1997 ).

Experimental

Crystal data

C₁₀H₁₃Br₂N
M_r = 307.03
Monoclinic, C 2/c
a = 17.566 (4) Å
b = 4.6083 (9) Å
c = 29.023 (6) Å
β = 98.93 (3)°
V = 2320.8 (8) Å³
Z = 8
Mo Kα radiation
μ = 6.94 mm⁻¹
T = 298 K
0.10 × 0.03 × 0.03 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.910, T_max = 1.000
9142 measured reflections
2633 independent reflections
1286 reflections with I > 2σ(I)
R_int = 0.117

Refinement

R[F² > 2σ(F²)] = 0.069
wR(F²) = 0.187
S = 0.98
2633 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.80 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N1ⁱ	0.86	2.53	3.181 (7)	134
N1—H1A⋯Br1	0.86	2.68	3.095 (5)	111
N1—H1B⋯Br2	0.86	2.64	3.074 (5)	113
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810047410/dn2624sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810047410/dn2624Isup2.hkl

checkCIF report

Comment top

In recent years there has been a rapidly increasing interest in the construction of various kinds of supramolecular systems for understanding molecular self-assembly principles and for designing molecular recognition devices (Fender et al., 2002; Kryatova et al., 2004; Pedersen, 1967). The supramolecular system generally refers to an assembly of molecules which are not covalently connected but assembled by other weak intermolecular interactions, such as hydrogen bonds (Grabowski, 2005; Lehn, 1995; Scheiner, 1997). We report here the crystal structure of the title compound, 2,6-dibromo-4-butylaniline.

In the title compound (Fig.1), the N atom of the amine group is essentially coplanar with the phenyl ring, with a r.m.s. deviation of 0.004 Å. This planar conformation might be resulting from weak intramolecular N-H···Br hydrogen bonds (Table 1). The butyl group is twisted with respect to the phenyl ring resulting in torsion angles of -179.1 (7)° for C9—C8—C7—C6 and -174.7 (7)° for C7—C8—C9—C10. Bond lengths and angles lie within normal ranges.

In the crystal structure, the organic molecules are linked to form a one-dimensional chain along b axis by N1—H···N1 hydrogen bonds (Table 1, Fig.2).

Related literature top

For supramolecular self-assembly chemisty, see: Fender et al. (2002); Grabowski (2005); Kryatova et al. (2004); Lehn (1995); Pedersen (1967); Scheiner (1997).

Experimental top

2,6-dibromo-4-butylaniline (3 mmol) was dissolved in ethanol (20 ml). The solution was allowed to evaporate to obtain colourless block-shaped crystals of the title compound.

Structure description top

In the crystal structure, the organic molecules are linked to form a one-dimensional chain along b axis by N1—H···N1 hydrogen bonds (Table 1, Fig.2).

For supramolecular self-assembly chemisty, see: Fender et al. (2002); Grabowski (2005); Kryatova et al. (2004); Lehn (1995); Pedersen (1967); Scheiner (1997).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Partial packing view of the title compound along the a axis. H atoms not involved in hydrogen bonding (dashed lines) have been omitted for clarity. [Symmetry code: (i) -x+1/2, y-1/2, -z+1/2]

2,6-Dibromo-4-butylaniline top

Crystal data top

C₁₀H₁₃Br₂N	F(000) = 1200
M_r = 307.03	D_x = 1.757 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2633 reflections
a = 17.566 (4) Å	θ = 3.4–27.5°
b = 4.6083 (9) Å	µ = 6.94 mm⁻¹
c = 29.023 (6) Å	T = 298 K
β = 98.93 (3)°	Block, colourless
V = 2320.8 (8) Å³	0.10 × 0.03 × 0.03 mm
Z = 8

Data collection top

Rigaku Mercury2 diffractometer	2633 independent reflections
Radiation source: fine-focus sealed tube	1286 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.117
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.4°
CCD profile fitting scans	h = −22→22
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −5→5
T_min = 0.910, T_max = 1.000	l = −37→37
9142 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.187	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.063P)²] where P = (F_o² + 2F_c²)/3
2633 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.80 e Å⁻³
0 restraints	Δρ_min = −0.60 e Å⁻³

Crystal data top

C₁₀H₁₃Br₂N	V = 2320.8 (8) Å³
M_r = 307.03	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 17.566 (4) Å	µ = 6.94 mm⁻¹
b = 4.6083 (9) Å	T = 298 K
c = 29.023 (6) Å	0.10 × 0.03 × 0.03 mm
β = 98.93 (3)°

Data collection top

Rigaku Mercury2 diffractometer	2633 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1286 reflections with I > 2σ(I)
T_min = 0.910, T_max = 1.000	R_int = 0.117
9142 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.069	0 restraints
wR(F²) = 0.187	H-atom parameters constrained
S = 0.98	Δρ_max = 0.80 e Å⁻³
2633 reflections	Δρ_min = −0.60 e Å⁻³
118 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.14631 (4)	0.22239 (18)	0.32043 (3)	0.0773 (4)
Br2	0.46385 (4)	0.3101 (2)	0.30522 (3)	0.0848 (4)
C3	0.3061 (3)	0.2877 (13)	0.31725 (18)	0.0482 (17)
C6	0.3272 (5)	0.6955 (13)	0.3926 (2)	0.0576 (18)
C2	0.2466 (3)	0.3776 (13)	0.3404 (2)	0.0512 (16)
C4	0.3781 (3)	0.4182 (15)	0.33358 (18)	0.0533 (16)
C5	0.3878 (4)	0.6137 (13)	0.36996 (19)	0.0544 (17)
H5	0.4363	0.6931	0.3796	0.065*
C1	0.2562 (4)	0.5724 (16)	0.3769 (2)	0.0596 (18)
H1	0.2141	0.6218	0.3912	0.072*
N1	0.2963 (3)	0.1017 (12)	0.28006 (16)	0.0621 (15)
H1A	0.2513	0.0335	0.2698	0.074*
H1B	0.3351	0.0530	0.2670	0.074*
C8	0.3747 (5)	0.7421 (14)	0.4792 (2)	0.076 (2)
H8A	0.3404	0.5851	0.4847	0.091*
H8B	0.4235	0.6566	0.4749	0.091*
C7	0.3402 (4)	0.8986 (16)	0.43391 (19)	0.072 (2)
H7A	0.2914	0.9862	0.4380	0.086*
H7B	0.3747	1.0530	0.4277	0.086*
C9	0.3877 (4)	0.9328 (19)	0.5218 (2)	0.086 (2)
H9A	0.4182	1.0995	0.5155	0.104*
H9B	0.3384	1.0034	0.5282	0.104*
C10	0.4278 (5)	0.7778 (17)	0.5637 (2)	0.102 (3)
H10A	0.4352	0.9084	0.5898	0.153*
H10B	0.4769	0.7094	0.5577	0.153*
H10C	0.3971	0.6160	0.5707	0.153*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0492 (5)	0.0947 (7)	0.0848 (6)	−0.0081 (4)	0.0005 (4)	0.0069 (4)
Br2	0.0537 (6)	0.1252 (9)	0.0770 (6)	−0.0047 (4)	0.0148 (4)	−0.0111 (4)
C3	0.046 (4)	0.059 (4)	0.039 (3)	0.001 (3)	0.004 (3)	0.008 (3)
C6	0.080 (5)	0.046 (4)	0.043 (4)	0.008 (4)	−0.004 (3)	0.005 (3)
C2	0.055 (4)	0.045 (4)	0.052 (4)	−0.004 (3)	0.002 (3)	0.008 (3)
C4	0.047 (4)	0.066 (5)	0.044 (3)	0.001 (3)	−0.003 (3)	0.000 (3)
C5	0.058 (4)	0.057 (4)	0.044 (4)	−0.004 (3)	−0.004 (3)	0.010 (3)
C1	0.054 (5)	0.076 (5)	0.051 (4)	0.011 (4)	0.014 (3)	0.017 (4)
N1	0.057 (3)	0.075 (4)	0.049 (3)	−0.005 (3)	−0.008 (2)	−0.008 (3)
C8	0.094 (6)	0.073 (5)	0.059 (4)	0.018 (4)	0.010 (4)	−0.004 (4)
C7	0.099 (6)	0.062 (5)	0.051 (4)	−0.009 (4)	0.002 (4)	0.000 (4)
C9	0.112 (6)	0.091 (6)	0.054 (4)	0.011 (5)	0.005 (4)	−0.014 (4)
C10	0.104 (7)	0.146 (9)	0.050 (4)	0.024 (5)	−0.008 (4)	−0.009 (5)

Geometric parameters (Å, º) top

Br1—C2	1.906 (6)	N1—H1B	0.8600
Br2—C4	1.891 (6)	C8—C9	1.504 (9)
C3—N1	1.368 (7)	C8—C7	1.539 (9)
C3—C2	1.392 (8)	C8—H8A	0.9700
C3—C4	1.414 (8)	C8—H8B	0.9700
C6—C1	1.382 (9)	C7—H7A	0.9700
C6—C5	1.387 (9)	C7—H7B	0.9700
C6—C7	1.510 (9)	C9—C10	1.491 (10)
C2—C1	1.379 (8)	C9—H9A	0.9700
C4—C5	1.378 (8)	C9—H9B	0.9700
C5—H5	0.9300	C10—H10A	0.9600
C1—H1	0.9300	C10—H10B	0.9600
N1—H1A	0.8600	C10—H10C	0.9600

N1—C3—C2	123.7 (5)	C7—C8—H8A	108.6
N1—C3—C4	121.9 (5)	C9—C8—H8B	108.6
C2—C3—C4	114.3 (5)	C7—C8—H8B	108.6
C1—C6—C5	116.9 (6)	H8A—C8—H8B	107.6
C1—C6—C7	122.2 (7)	C6—C7—C8	112.2 (6)
C5—C6—C7	120.9 (6)	C6—C7—H7A	109.2
C1—C2—C3	123.6 (6)	C8—C7—H7A	109.2
C1—C2—Br1	118.3 (5)	C6—C7—H7B	109.2
C3—C2—Br1	118.0 (5)	C8—C7—H7B	109.2
C5—C4—C3	122.1 (6)	H7A—C7—H7B	107.9
C5—C4—Br2	119.6 (5)	C10—C9—C8	112.6 (7)
C3—C4—Br2	118.2 (4)	C10—C9—H9A	109.1
C4—C5—C6	121.9 (6)	C8—C9—H9A	109.1
C4—C5—H5	119.0	C10—C9—H9B	109.1
C6—C5—H5	119.0	C8—C9—H9B	109.1
C2—C1—C6	121.1 (6)	H9A—C9—H9B	107.8
C2—C1—H1	119.4	C9—C10—H10A	109.5
C6—C1—H1	119.4	C9—C10—H10B	109.5
C3—N1—H1A	120.0	H10A—C10—H10B	109.5
C3—N1—H1B	120.0	C9—C10—H10C	109.5
H1A—N1—H1B	120.0	H10A—C10—H10C	109.5
C9—C8—C7	114.7 (6)	H10B—C10—H10C	109.5
C9—C8—H8A	108.6

N1—C3—C2—C1	−177.8 (6)	C1—C6—C5—C4	−0.2 (9)
C4—C3—C2—C1	−1.3 (8)	C7—C6—C5—C4	176.9 (6)
N1—C3—C2—Br1	2.2 (8)	C3—C2—C1—C6	0.8 (10)
C4—C3—C2—Br1	178.7 (4)	Br1—C2—C1—C6	−179.1 (5)
N1—C3—C4—C5	177.6 (5)	C5—C6—C1—C2	0.0 (9)
C2—C3—C4—C5	1.1 (8)	C7—C6—C1—C2	−177.1 (6)
N1—C3—C4—Br2	−4.1 (8)	C1—C6—C7—C8	97.6 (8)
C2—C3—C4—Br2	179.3 (4)	C5—C6—C7—C8	−79.4 (8)
C3—C4—C5—C6	−0.3 (9)	C9—C8—C7—C6	−179.1 (6)
Br2—C4—C5—C6	−178.6 (4)	C7—C8—C9—C10	−174.7 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N1ⁱ	0.86	2.53	3.181 (7)	134
N1—H1A···Br1	0.86	2.68	3.095 (5)	111
N1—H1B···Br2	0.86	2.64	3.074 (5)	113

Symmetry code: (i) −x+1/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₃Br₂N
M_r	307.03
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	17.566 (4), 4.6083 (9), 29.023 (6)
β (°)	98.93 (3)
V (Å³)	2320.8 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	6.94
Crystal size (mm)	0.10 × 0.03 × 0.03

Data collection
Diffractometer	Rigaku Mercury2
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.910, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	9142, 2633, 1286
R_int	0.117
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.069, 0.187, 0.98
No. of reflections	2633
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.80, −0.60

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N1ⁱ	0.86	2.53	3.181 (7)	134.0
N1—H1A···Br1	0.86	2.68	3.095 (5)	111
N1—H1B···Br2	0.86	2.64	3.074 (5)	113

Symmetry code: (i) −x+1/2, y−1/2, −z+1/2.

Acknowledgements

This work was supported by a School Start-up Grant to LZ.

References

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